Novel compositions of matter and methods for preparing them



United States Patent Office 2,993,918 Patented July 25, 1961 7 2,993,918NOVEL COMPOSITIONS F MATTER AND METHODS FOR PREPARING THE-M Hans S.Mannheimer, 905 West End Ave., New York, N.Y., assignor to John J.McCabe, Jr., and Hans S. Mannheimer, joint venturers No Drawing.Original application Apr. 2, 1956, Ser. No. 575,300, now Patent No.2,781,349, dated Feb. 12, 1957. Divided and this application Dec. 19,1956, Ser. No. 629,246

3 Claims. (Cl. 260-401) This invention relates to novel compositions andto methods for producing them. In one of its more specific aspects, theinvention is directed to novel derivatives of surface active agentswhich behave anionically at pH above 7, and which I shall hereinafterrefer to as surface active agents behaving anionically at pH above 7.

Said surface active agents behaving anionically at pH above 7 have beenfound usefill as detergent, foaming, wetting, emulgating, emulsifyingand dispersing agents. They are surface active agents, and serve as eX-cellent synthetic detergents, dye assistants and softeners in thetextile and related fields.

Said surface acting agents behaving anionically at pH above 7, employedas starting materials in the practice of this invention, are of thefollowing general Formula I in which R is a hydrocarbon radical of 4-18carbon atoms; Q is selected from the class consisting of. (e) hydrogen,(f) R and (h) R COOM; R is selected from the class consisting of (j)aliphatic hydrocarbon and hydroxy substituted hydrocarbon groups of 14carbon atoms, and R is an alkyl radical of 1-4 carbon atoms, and R isselected from the group consisting of hydrogen and alkyl and hydroxysubstituted alkyl radicals of 1-4 carbon atoms and M is an alkali metal.

It is understood, of course, that the terminal OH groups in any of theaforesaid compounds may be ONa because they are obvious equivalents, andone may mean the other wherever it occurs herein.

Said compounds of Formula I may be produced in a number of differentways:

For example, .1 mole of a diamine, such as ethylene diamine (NH C H NHmay be reacted with 1 mole of a monocarboxylic acid, R'-COOH, examplesof which are set forth in my US. Patent 2,528,378. The reaction may becontinued under the conditions 'set forth in Example 9 of said 'p'atentuntil only 1 mole of water has been formed to provide a compound 1 moleof said last identified compound may be reacted with 2 moles of oneofsaid monohalomonocarboxylic acids of 1-4 carbon atoms in their radicalsattached to the COOH groups thereof, together with about 4.5- moles ofan alkali metal hydroxide to provide the following cornpound IB-l:

' F m-o'o OM R-C ONHC2H4N Ri -000M Examples of some of the otherdiamines which may I be employed to produce starting materials which maybe- The following are specific illustrative examples of some of thestarting materials of Formula I and the method for preparing them, allparts being given by weight unless otherwise specified:

EXAMPLE A 1 mole of lauric fatty acid (C H COOH) and 1 mole ofethylenediamine (NI-I C H NH are added together and then heated in thepresence of an inert solvent such as toluol in amounts sufiicient todissolve the same. This solution is maintained at a temperature ofapproximately C. This heating is carried out under a condenser throughwhich pass vapors which consist of some of the solvent and water ofreaction as well as small amounts of unreacted amine. These products arecaught in a collector from which the water of reaction is removed andthe condensed toluol and collected amine are returned to the reactingvessel. The temperature of the mass is maintained at 110 C. under theaforesaid conditions until 0.9mole of water is collected. Then thetoluol and 0.1 additional mole of water are removed under heat and highvacuum. The resultant mass is essentially:

Then 1 mole of this compound is mixed with l and 2 moles respectively ofmonochloracetic acid and externally heated and the temperature thereofmaintained at C. until a one part sample thereof in 100 parts of anaqueous solution of NaOH having a pH of about 9 provides a clearsolution. Then there is added thereto an aqueous solution of 2 and 4moles of NaOH and the mass is heated to approximately 80-90 C. whereuponthe following compounds are produced and are hereinafter known asProduct IB-l and IB-2 of the following respective formulas:

H 011E 36 ONHCzHtN CH2-COON5 and f oHPoooNa C11Hg50 ONHCgHlN OH2C O ONaEXAMPLE B Employing the same procedure as that set forth .in Example A,except that for the 1 mole of the ethylene diamine there are substituted1 mole of each of the Reactants H-J, there are provided compounds whichare the same as Products IB-l, and IB-2, and except that the C H groupsthereof are replaced by C H C H C3H5OH" groups respectively, to provideProducts IB- 3'to EXAMPLE (3 Employ the same procedure'as that set forthin Example A, but employing 1 mole of Reactant L instead of the ethylenediamine and using only a single mole of the A) a monochloracetic acid,there are provided the following compounds hereinafter known as ProductsIB9:

Ell CzHs CuHzsG ONCzHlN CHz-C O ONa Prior to this invention, it wasknown that cation surface active agents and anionic surface activeagents when together in aqueous solution resulted in the production orformation of water insoluble compounds, and that adding an anionicsurface active agent to an aqueous solution of another anionic surfaceactive agent resulted in a mere physical combination of said agents andthat no reaction would occur between them.

Said compounds of Formula I, normally behave anionically in aqueoussolutions having a pH above 7, and consequently it was expected thatwhen in aqueous solution together with anionic surface agents that theywould be combined physically only and that no chemical reaction wouldoccur therebetween. In the course of my experimentations, I havediscovered that they could be reacted with certain anionic surfaceactive agents at a pH above 7 to produce water-soluble reactionproducts. Not only did I make said discovery, but I further discoveredthat water solutions of such reaction products had viscosities greaterthan corresponding aqueous solutions of compounds of Formula I, and alsoexhibited better foaming characteristics than did said compounds in verylow dilutions under extreme water hardness conditions. Said reactionproducts are non-toxic and non-irritating to the human skin. They havebeen found eminently useful as general utility detergents, such as forcar washing, dish washing, clothes washing, etc. Said compounds ofFormula I and compounds of Formulas IIA-IID when, any one of them aloneor a combination of two or more of them in mere physical mixture areused as components of shampoos caused varying degrees of irritation andmarked stinging of the eyes when such shampoos were used and watersolutions thereof accidentally reached the eyes. I have furtherdiscovered that the reaction products of this invention causedpractically no irritation or stinging of the eyes when so employed.

, According to this invention, one or a combination of two or more ofcompounds of the general structural Formula I are reacted with one or acombination of two or more anionic surface active agents of thefollowing general structural Formulas IIA-IID which are broadly referredto as Formula II, to provide novel, water-soluble compounds having thefollowing general structural formula, which are broadly referred to asFormula III, all having high wetting, detergency and surface activeproperties and capable of providing voluminous and stable foams inaqueous solutions, and which solutions are substantially non-irritatingto the skin and eyes of normal human beings.

Compounds of Formulas IIA-IID respectively are detergent sulfonic acidsalts and sulfate salts which may be represented as follows:

wherein M has heretofore been defined and G is selected from the groupconsisting of:

R-C -N-Rt-X Rr-Z(Cz 4 )xS0s Rr-X Rr-COORkX 2 Compounds of Formula IIImay be represented as follows:

Formula Ill 1 Q1 RC0--1 I-R7N H (it Ri-(Jo OM According to thisinvention, I react a compound of Formula I with a compound of Formula IIto provide the novel and highly useful compounds of Formula III. Ingeneral, this reaction is carried out in a solution containing compoundsI and II and to which a quantity of an acidic agent such as a strongmineral acid, as for example hydrochloric, sulphuric or its equivalent,has been added to lower the pH of the solution to a value ofapproximately 7 to approximately 9 and while maintaining the mass at atemperature between approximately l00-200 F. In this reaction under theaforesaid conditions, the compounds of Formula III are produced, saidcompounds having high water solubility. Such compounds of Formula IIIhave an unexpected extremely high water-solubility, while thecorresponding salts of cationic compounds are water-insoluble. Theresultant aqueous solution can be used directly as a surface activeagent, wetting agent or detergent for the purposes indicated for thecompounds of Formula I. While the quantities of the compound of FormulaI and compound of Formula II may be equimolecular for good yield ofcompounds of Formula HI, I may employ an excess of either, and ingeneral the mole ratio of a compound of Formula I to compound of Formula11 may be 2 moles of the former to 1-3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out anaspect of this invention is to first dissolve a compound of Formula I inwater and then the pH thereof is adjusted to approximately 12-13(measured electrically) by the addition of aqueous caustic soda ifrequired so that when a compound of Formula II is added thereto, the pHof the solution of I and II will be at least 10 and generally 10.5-11.The temperature of said solution is raised to -200 F. and preferably infactory practice to approximately 140 F. Then a quantity of a compoundof Formula II is dissolved in water in a separate container and thissolution is added to said first solution and the mass is maintained insaid temperature range while being constantly stirred, and an acidicagent is added thereto to reduce the pH thereof to a value below 10 andin the range of approximately 7 to 9, and preferably of approximately8.2 to approximately 8.7. At the end of the acidic agent addition, thestirring is continued and the temperature of the mass maintained forabout 10-20 minutes after which the solution is allowed to cool and is afinished product.

The following are specific examples merely given by way of illustratingthe invention and are not to be taken by way of limitation, all partsbeing given by weight unless otherwise specified.

EXAMPLE 1 An aqueous solution of 420 parts of Product 13-4, in 620 partsof water is heated to approximately 140 F. and its pH adjusted to 12-13(measured electrically) by the addition of caustic soda. While beingconstantly stirred and maintained at that temperature there is added asolution of 230 parts of:

in 350 parts of water. Then while stirring and temperature ismaintained, there is added thereto sufficient hydrochloric acid solution(32%) whereby the pH of the mass s lowered to a value in the range of8.2 to 8.7. Stirring 15' continued and the temperature is maintained forabout 10 minutes more. The resultant product is a solution of the novelreaction product of the following formula:

CH -COONa CuHgr-G ONHCsHs-N H CHz-G 0 ONa Como" EXAMPLE 2 Employ thesame procedure and components as set forth in Example 1, except thatonly parts of the salt of the sulfonic acid are employed' In instance,the resultant product is a solution of the novel reaction prodnet ofExample 1 together with unreacted Product IB-4 used in the approximateproportion of 2 to 1.

Employ the same procedure as that set forth in Example l, but employ thecomponents set forth in the following Examples 3-5 on, the quantity ofhydrochloric acid solution (32%) is variable to lower the pH to thevalues indicated to obtain the novel reaction products of Examples 3-5on.

EXAMPLES 3-4 320 parts of Product IB-l and 480 pants of IB-2respectively in 600 parts of water. 400 parts respectively of lauryltaurate sodium salt:

and of lauryl sulfanilamide sodium salt:

C H23-CO-NH-CgH4SO3Na Formulas of respective novel reaction products:

CHr-C ONE CHg-C O ONa EXAMPLES 5 ON Employing 1 mole proportion of allof the other specific compounds of Formula I respectively in about oneand one-half times its weight of water and 1 mole proportion of any ofthe specific Formulas IIA-IID respectively in one and one-half times itsweight of water, there are produced literally hundreds of compounds ofFormula III which differ from those of Examples 1-4 and such compoundsare also specific examples of illustrative novel reaction products ofthis invention. Other examples of Formulas IIa-IID are:

It is also to be understood that any of the specific products of the IBseries which are shown herein merely as illustrative examples of thestarting materials of Formula I which may be reacted with any of thespecific sulfate or sul-fonate salts which are shown herein merely asillustrative examples of reactants of Formula II to produce novelcompounds of Formula III.

It is to be understood that, as to compounds of Formulas IIA, IIC andIII) and also as to novel reaction products thereof when either S0 or080 is used in the specifications or claims, it is meant to indicateeither one or the other because of their obvious equivalency; it is alsoto be understood that the use of Na in the specification and claims ismeant to indicate any of the other alkali metals because of theirobvious equivalency; and it is also to be understood that the CONHlinkage when part of compounds in the specification and claims is meantto indicate either it or NHCO because of their obvious equivalency.

It is also to be understood that instead of first adjusting the pH ofthe compound of Formula I to 12-13 before the addition of the compoundof Formula II, any other method may be employed to obtain the conditionwhereby the pH of the solution of I and II is at least 10 and preferably10.5-11 before the addition of the acidic agent to lower the pH of themass to approximately 7 to approximately 9. For example, I and II may bedissolved together and this solution may by the addition of caustic sodawhen required have its pH adjusted to at least 10, and then at -200 F.is ready for the addition of the acidic agent to lower its pH toapproximately 7 to approximately 9. If desired, the required amount ofacidic agent may be added either before or after the solution at pH ofat least 10 is brought to a temperature in the range of 100-200 F.

This application is a continuation-in-part of my copending application585,940 of April 21, 1956 (Patent 2,781,350) which in turn is acontinuation in part of now abandoned application 413,721 of March 2,1954; copending application 592,749 of June 21, 1956 (Patent 2,781,358)which in turn is a continuation in part of now abandoned application425,307 of April 23, 1954; of copending application 473,043 of December3, 1954 (2,781,357) and copending application 623,526 of November 21,1956 (2,781,351) in turn a continuation in part of 565,538 of February15, 1956 and now abandoned, in turn a continuation in part of nowabondoned application 481,703 of January 13, 1955.

This application is a division of my application Serial No. 575,300 ofApril 2, 1956.

Since certain changes in carrying out the aforesaid processes andcertain modifications in the compositions which embody the invention maybe made without departing from its scope, it is intended that all mattercontained in the description shall be interpreted as illustrative andnot in a limiting sense.

It is also to be understood that the following claims are intended tocover all the generic and specific features of the invention hereindescribed, and all statements of the scope of the invention which as amatter of language might be said to fall therebetween.

I claim:

1. A compound selected from the class consisting of salts of detergentsulfonic acids and detergent sulfates respectively and an amphotericsurface active agent, said compound having the following formula:

Rz-COOM in which R is a hydrocarbon radical of 4-18 carbon atoms; each Ris selected from the class consisting of (a) alkylene groups of 1-4carbon atoms and (b) bydroxy substituted alkylene groups of 1-4 carbonatoms; Q is selected from the class consisting of (c) hydrogen, (d)monovalent alkyl radicals of 1-4 carbon atoms and radicals of 1-4 carbonatoms; G is selected from the class consisting of sulfonic acid andsulfate radicals of 5 detergent sulfonic acid salts and sulfate salts;and M is an alkali metal.

2. A compound defined in claim 1, in which Q is hydrogen and R ishydrocarbon of 14 carbon atoms.

3, A compound defined in claim 1 in which Q, is 10 CH COOM and R COOM isCH COOM.

ReferencesCited in the file of this patent UNITED STATES PATENTSSch'oeller et a1. Dec. 28, 1937 Weichselbaum Mar. 7, 1950 Vitalis Sept.13, 1955 Mannheimer Dec. 4, 1956 Mannheimer Feb. 12, 1957 MannheimerFeb. 12, 1957 Mannheimer Feb. 12, 1957 Mannheimer Feb. 12, 1957

1. A COMPOUND SELECTED FROM THE CLASS CONSISTING OF SALTS OF DETERGENTSULFONIC ACIDS AND DETERGENT SULFATES RESPECTIVELY AND AN AMPHOTERICSURFACE ACTIVE AGENT, SAID COMPOUND HAVING THE FOLLOWING FORMULA: